CN112447962A - Precursor for doped lithium ion battery, positive electrode material and preparation methods of precursor and positive electrode material - Google Patents
Precursor for doped lithium ion battery, positive electrode material and preparation methods of precursor and positive electrode material Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 78
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000007774 positive electrode material Substances 0.000 title claims description 30
- 239000011572 manganese Substances 0.000 claims abstract description 92
- 239000011777 magnesium Substances 0.000 claims abstract description 78
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 65
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000000975 co-precipitation Methods 0.000 claims abstract description 19
- 230000002285 radioactive effect Effects 0.000 claims abstract description 14
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 29
- 229910052744 lithium Inorganic materials 0.000 claims description 29
- 239000012266 salt solution Substances 0.000 claims description 27
- 239000012298 atmosphere Substances 0.000 claims description 22
- 229910013716 LiNi Inorganic materials 0.000 claims description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 12
- 229910001437 manganese ion Inorganic materials 0.000 claims description 12
- 229910001453 nickel ion Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229940044175 cobalt sulfate Drugs 0.000 claims description 10
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 10
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 10
- 229940099596 manganese sulfate Drugs 0.000 claims description 10
- 239000011702 manganese sulphate Substances 0.000 claims description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 description 25
- 230000001276 controlling effect Effects 0.000 description 12
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 11
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 11
- 239000012697 Mn precursor Substances 0.000 description 10
- 230000002431 foraging effect Effects 0.000 description 10
- 229940053662 nickel sulfate Drugs 0.000 description 9
- 229960003390 magnesium sulfate Drugs 0.000 description 7
- 238000012360 testing method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229940091250 magnesium supplement Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a nickel-cobalt-manganese precursor for a doped lithium ion battery, which is a radioactive metal hydroxide and has the chemical expression as follows: ni0.7Co0.1Mn0.2‑xMgx(OH)2Wherein x is more than or equal to 0.02 and less than or equal to 0.04. The invention also discloses a preparation method of the nickel-cobalt-manganese precursor. According to the invention, the Mg doping element is directly added in the coprecipitation process, so that the doping element can be uniformly distributed in the precursor particles, the modification effect of the doping element is effectively exerted, and the magnesium doping is beneficial to forming a good layered structure, enhancing the structural stability of the material and improving the cycle performance of the high-nickel ternary material.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a precursor and a positive electrode material for a doped lithium ion battery, and preparation methods of the precursor and the positive electrode material.
Background
In the face of the increasing energy demand due to the continuous development of science and technology and the environmental problems caused by the use of fossil energy, Lithium Ion Batteries (LIBs) are distinguished by the advantages of high specific energy, small self-discharge, high open circuit voltage, no memory effect, long cycle life, small environmental pollution and the like; the anode material is a key component of the lithium ion battery, not only takes part in electrochemical reaction as an electrode material, but also serves as a lithium ion source, and determines the safety, performance, cost and service life of the battery to a great extent; with the continuous expansion and extension of the application scenes of the lithium ion battery, the capacity requirement of the lithium ion battery is higher and higher. The layered nickel-cobalt-manganese ternary composite cathode material is a novel lithium ion battery cathode material which is mainstream at present, and under the conventional working voltage of a 4.4V lithium ion battery, the higher the content of nickel in the cathode material is, and the larger the specific capacity of the material is. Under such circumstances, high nickel ternary positive electrode materials represented by 622, 712, 811, and the like have attracted more and more attention and have become hot spots of research in recent years. However, due to ternary LiNi1-x-yCoxMnyO2The characteristics of the self structure of the anode material are that the thermal stability, the cycle performance and the rate performance of the material are not satisfactory with the continuous increase of the nickel content. In order to improve the comprehensive electrochemical performance of the high-nickel ternary material, researchers have proposed various methods, the methods commonly used at present are mainly ion doping and surface coating, and relatively few researches have focused on improving some problems of the high-nickel ternary material by regulating the internal structure of the material.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a nickel-cobalt-manganese precursor for a doped lithium ion battery, which solves the problems of poor stability, cycle performance and rate capability and low specific discharge capacity of the existing materials; the invention also aims to provide a preparation method of the precursor, a positive electrode material prepared from the precursor and a preparation method of the positive electrode material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows: a nickel-cobalt-manganese precursor for a doped lithium ion battery is a radioactive metal hydroxide, and has the chemical expression: ni0.7Co0.1Mn0.2-xMgx(OH)2Wherein x is more than or equal to 0.02 and less than or equal to 0.04.
Preferably, the average particle size of the nickel-cobalt-manganese precursor for the doped lithium ion battery is 15-25 μm.
The second technical scheme of the invention is realized as follows: the precursor is used as the anode material for the lithium ion battery, and the molecular formula of the anode material is LiNi0.7Co0.1Mn0.2-xMgxO2Wherein x is more than or equal to 0.02 and less than or equal to 0.04.
The third technical scheme of the invention is realized as follows: a preparation method of a nickel-cobalt-manganese precursor for a doped lithium ion battery is characterized by comprising the following steps:
step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.2-x: x (x is more than or equal to 0.02 and less than or equal to 0.04) is fully mixed with nickel salt, cobalt salt, manganese salt and magnesium salt to prepare a mixed salt solution for later use;
step 2, respectively adding the mixed salt solution, the alkali solution and the ammonia water in the step 1 into a reaction kettle through a metering pump in an inert gas atmosphere, and stirring for coprecipitation reaction;
and 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle to an ageing tank for ageing, and then centrifugally washing and drying to obtain the radial nickel-cobalt-manganese precursor Ni0.7Co0.1Mn0.2-xMgx(OH)2。
Preferably, in the step 1, the nickel salt is at least one of nickel chloride, nickel sulfate and nickel nitrate; the cobalt salt is at least one of cobalt chloride, cobalt sulfate and cobalt nitrate; the manganese salt is at least one of manganese chloride, manganese sulfate and manganese nitrate; the magnesium salt is at least one of magnesium chloride, magnesium sulfate and magnesium nitrate.
Preferably, in the step 1, the concentration of nickel, cobalt, manganese and magnesium ions in the mixed salt solution is 1-3 mol/L.
Preferably, in the step 2, the molar concentration of the alkali solution is 3-5 mol/L, and the molar concentration of the ammonia water is 8-12 mol/L; the alkali in the alkali solution is sodium hydroxide or potassium hydroxide.
Preferably, in the step 2, the reaction temperature of the coprecipitation reaction is 40-70 ℃, the reaction pH is 11-12.5, the stirring speed is 150-250 rpm, and the reaction time is 60-90 h.
The fourth technical scheme of the invention is realized as follows: a preparation method of a nickel-cobalt-manganese positive electrode material for a doped lithium ion battery is characterized by comprising the steps of mixing a precursor prepared by the preparation method with a lithium source, and sintering at a high temperature in an atmosphere furnace filled with oxygen to obtain the nickel-cobalt-manganese positive electrode material LiNi for the doped lithium ion battery0.7Co0.1Mn0.2-xMgxO2。
Preferably, the proportion of lithium is 1.05, the sintering temperature is 700-900 ℃, and the sintering time is 9-14 h.
According to the invention, the Mg doping element is directly added in the coprecipitation process, so that the doping element can be uniformly distributed in the precursor particles, the modification effect of the doping element is effectively exerted, and the magnesium doping is beneficial to forming a good layered structure, enhancing the structural stability of the material and improving the cycle performance of the high-nickel ternary material. By controlling the synthesis process of the precursor, primary particles are directionally arranged to form a radial structure from inside to outside, and the precursor particles grow radially from inside to outside, so that the lithium salt is favorably diffused in the precursor particles in the sintering process for preparing the anode material, the reaction is more sufficient, the prepared ternary anode material can form a lithium ion diffusion channel from inside to outside, the radial structure is favorable for the extraction and the insertion of lithium ions, and the particle structure is more stable, so that the excellent electrochemical performance is shown.
Drawings
FIG. 1 is an SEM image of a Ni-Co-Mn precursor obtained in example 1 of the present invention;
fig. 2 is an SEM image of the nickel-cobalt-manganese precursor obtained in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a nickel-cobalt-manganese precursor for a doped lithium ion battery, which is a radioactive metal hydroxide and has the chemical expression as follows: ni0.7Co0.1Mn0.2-xMgx(OH)2Wherein x is more than or equal to 0.02 and less than or equal to 0.04, and the average particle size of the nickel-cobalt-manganese precursor for the doped lithium ion battery is 15-25 mu m.
The embodiment of the invention also provides a positive electrode material for the lithium ion battery, which has the precursor, and the molecular formula of the positive electrode material is LiNi0.7Co0.1Mn0.2-xMgxO2Wherein x is more than or equal to 0.02 and less than or equal to 0.04.
The embodiment of the invention also provides a preparation method of the nickel-cobalt-manganese precursor for the doped lithium ion battery, which comprises the following steps:
step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.2-x: x (x is more than or equal to 0.02 and less than or equal to 0.04) is fully mixed with nickel salt, cobalt salt, manganese salt and magnesium salt to prepare a mixed salt solution for later use;
wherein the nickel salt is at least one of nickel chloride, nickel sulfate and nickel nitrate; the cobalt salt is at least one of cobalt chloride, cobalt sulfate and cobalt nitrate; the manganese salt is at least one of manganese chloride, manganese sulfate and manganese nitrate; the magnesium salt is at least one of magnesium chloride, magnesium sulfate and magnesium nitrate; the concentration of nickel, cobalt, manganese and magnesium ions in the mixed salt solution is 1-3 mol/L;
step 2, respectively adding the mixed salt solution, the alkali solution and the ammonia water in the step 1 into a reaction kettle through a metering pump in an inert gas atmosphere, and stirring for coprecipitation reaction;
wherein the molar concentration of the alkali solution is 3-5 mol/L, and the molar concentration of the ammonia water is 8-12 mol/L; the alkali in the alkali solution is sodium hydroxide or potassium hydroxide; the reaction temperature of the coprecipitation reaction is 40-70 ℃, the reaction pH is 11-12.5, the stirring speed is 150-250 rpm, and the reaction time is 60-90 h.
And 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle to an aging tank for aging, and then centrifugally washing and drying to obtain the radial nickel-cobalt-manganese precursor Ni with the granularity of 15-25 mu m0.7Co0.1Mn0.2-xMgx(OH)2。
The embodiment of the invention also provides a preparation method of the nickel-cobalt-manganese anode material for the doped lithium ion battery, which comprises the steps of mixing the precursor obtained by the preparation method with a lithium source, and sintering at high temperature in an atmosphere furnace filled with oxygen to obtain the nickel-cobalt-manganese anode material LiNi for the doped lithium ion battery0.7Co0.1Mn0.2-xMgxO2(ii) a Wherein the proportion of lithium is 1.05, the sintering temperature is 700-900 ℃, and the sintering time is 9-14 h.
After the scheme is adopted, the Mg doping element is directly added in the coprecipitation process, so that the doping element can be uniformly distributed in the precursor particles, the modification effect of the doping element is effectively exerted, the magnesium doping is beneficial to forming a good layered structure, the structural stability of the material is enhanced, and the cycle performance of the high-nickel ternary material is improved. By controlling the synthesis process of the precursor, primary particles are directionally arranged to form a radial structure from inside to outside, and the precursor particles grow radially from inside to outside, so that the lithium salt is favorably diffused in the precursor particles in the sintering process for preparing the anode material, the reaction is more sufficient, the prepared ternary anode material can form a lithium ion diffusion channel from inside to outside, the radial structure is favorable for the extraction and the insertion of lithium ions, and the particle structure is more stable, so that the excellent electrochemical performance is shown.
Example 1
1) Preparation of Ni-Co-Mn precursor for doped lithium ion battery0.7Co0.1Mn0.18Mg0.02(OH)2；
Step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.18: fully mixing nickel sulfate, cobalt sulfate, manganese sulfate and magnesium sulfate according to the proportion of 0.02(9:1) to prepare a mixed salt solution with the concentration of nickel, cobalt, manganese and magnesium ions being 2mol/L for later use;
step 2, respectively adding the mixed salt solution, a sodium hydroxide solution with the concentration of 4mol/L and ammonia water with the concentration of 10mol/L into a reaction kettle through a metering pump in the nitrogen atmosphere, controlling the pH of the system to be 11-12.5 in the feeding process, and then carrying out coprecipitation reaction for 75 hours at the temperature of 55 ℃ and the stirring speed of 200 rpm;
and 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle to an aging tank for aging, and then centrifugally washing and drying to obtain the radial nickel-cobalt-manganese precursor Ni with the granularity of 20 mu m0.7Co0.1Mn0.18Mg0.02(OH)2。
The precursor is radial as can be clearly seen in figure 1;
2) preparation of nickel-cobalt-manganese anode material LiNi for doped lithium ion battery0.7Co0.1Mn0.18Mg0.02O2：
The radioactive nickel-cobalt-manganese precursor Ni is0.7Co0.1Mn0.18Mg0.02(OH)2Mixing with lithium source, and sintering at 800 deg.C in an atmosphere furnace filled with oxygen for 11h to obtain doped lithium ionNickel-cobalt-manganese positive electrode material LiNi for battery0.7Co0.1Mn0.18Mg0.02O2(ii) a Wherein the proportion of lithium is 1.05.
Example 2
1) Preparation of Ni-Co-Mn precursor for doped lithium ion battery0.7Co0.1Mn0.18Mg0.02(OH)2；
Step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.18: fully mixing nickel sulfate, cobalt sulfate, manganese sulfate and magnesium sulfate according to the proportion of 0.02(9:1) to prepare a mixed salt solution with the concentration of nickel, cobalt, manganese and magnesium ions being 1mol/L for later use;
step 2, in an inert gas atmosphere, adding the mixed salt solution, a sodium hydroxide solution with the concentration of 3mol/L and ammonia water with the concentration of 8mol/L into a reaction kettle through a metering pump respectively, controlling the pH of the system to be 11-12.5 in the feeding process, and then carrying out coprecipitation reaction for 90 hours at the temperature of 40 ℃ and the stirring speed of 150 rpm;
and 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle to an aging tank for aging, and then centrifugally washing and drying to obtain a radial nickel-cobalt-manganese precursor Ni with the granularity of 15 mu m0.7Co0.1Mn0.18Mg0.02(OH)2。
The precursor is radial as can be clearly seen in figure 2;
2) preparation of nickel-cobalt-manganese anode material LiNi for doped lithium ion battery0.7Co0.1Mn0.18Mg0.02O2：
The radioactive nickel-cobalt-manganese precursor Ni is0.7Co0.1Mn0.18Mg0.02(OH)2Mixing with a lithium source, and sintering at high temperature for 14h in an atmosphere furnace with 700 ℃ and oxygen to obtain the nickel-cobalt-manganese positive electrode material LiNi for the doped lithium ion battery0.7Co0.1Mn0.18Mg0.02O2(ii) a Wherein the proportion of lithium is 1.05.
Example 3
1) Preparation of Ni-Co-Mn precursor for doped lithium ion battery0.7Co0.1Mn0.18Mg0.02(OH)2；
Step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.18: fully mixing nickel sulfate, cobalt sulfate, manganese sulfate and magnesium sulfate according to the proportion of 0.02(9:1) to prepare a mixed salt solution with the concentration of nickel, cobalt, manganese and magnesium ions being 3mol/L for later use;
step 2, in an inert gas atmosphere, adding the mixed salt solution, a sodium hydroxide solution with the concentration of 3-5 mol/L and ammonia water with the concentration of 5mol/L into a reaction kettle through a metering pump respectively, controlling the pH of the system to be 11-12.5 in the feeding process, and performing coprecipitation reaction for 60 hours at the temperature of 70 ℃ and the stirring speed of 250 rpm;
and 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle to an aging tank for aging, and then centrifugally washing and drying to obtain the radial nickel-cobalt-manganese precursor Ni with the granularity of 25 mu m0.7Co0.1Mn0.18Mg0.02(OH)2。
2) Preparation of nickel-cobalt-manganese anode material LiNi for doped lithium ion battery0.7Co0.1Mn0.18Mg0.02O2：
The radioactive nickel-cobalt-manganese precursor Ni is0.7Co0.1Mn0.18Mg0.02(OH)2Mixing with a lithium source, and sintering at high temperature for 9h in an atmosphere furnace with 900 ℃ and oxygen to obtain the nickel-cobalt-manganese positive electrode material LiNi for the doped lithium ion battery0.7Co0.1Mn0.18Mg0.02O2(ii) a Wherein the proportion of lithium is 1.05.
Example 4
1) Preparation of Ni-Co-Mn precursor for doped lithium ion battery0.7Co0.1Mn0.16Mg0.04(OH)2；
Step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.16: fully mixing nickel sulfate, cobalt sulfate, manganese sulfate and magnesium sulfate according to the proportion of 0.04(4:1) to prepare a mixed salt solution with the concentration of nickel, cobalt, manganese and magnesium ions being 2mol/L for later use;
step 2, in an inert gas atmosphere, adding the mixed salt solution, a sodium hydroxide solution with the concentration of 3mol/L and ammonia water with the concentration of 8mol/L into a reaction kettle through a metering pump respectively, controlling the pH of the system to be 11-12.5 in the feeding process, and then carrying out coprecipitation reaction for 90 hours at the temperature of 40-70 ℃ and the stirring speed of 150 rpm;
and 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle to an aging tank for aging, and then centrifugally washing and drying to obtain the radial nickel-cobalt-manganese precursor Ni with the granularity of 20 mu m0.7Co0.1Mn0.16Mg0.04(OH)2。
2) Preparation of nickel-cobalt-manganese anode material LiNi for doped lithium ion battery0.7Co0.1Mn0.16Mg0.04O2：
The radioactive nickel-cobalt-manganese precursor Ni is0.7Co0.1Mn0.16Mg0.04(OH)2Mixing with a lithium source, and sintering at high temperature for 14h in an atmosphere furnace with 700 ℃ and oxygen to obtain the nickel-cobalt-manganese positive electrode material LiNi for the doped lithium ion battery0.7Co0.1Mn0.16Mg0.04O2: (ii) a Wherein the proportion of lithium is 1.05.
Example 5
1) Preparation of Ni-Co-Mn precursor for doped lithium ion battery0.7Co0.1Mn0.16Mg0.04(OH)2；
Step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.16: fully mixing nickel sulfate, cobalt sulfate, manganese sulfate and magnesium sulfate according to the proportion of 0.04(4:1) to prepare a mixed salt solution with the concentration of nickel, cobalt, manganese and magnesium ions being 2mol/L for later use;
step 2, in an inert gas atmosphere, adding the mixed salt solution, a sodium hydroxide solution with the concentration of 3-5 mol/L and ammonia water with the concentration of 5mol/L into a reaction kettle through a metering pump respectively, controlling the pH of the system to be 11-12.5 in the feeding process, and performing coprecipitation reaction for 60 hours at the temperature of 70 ℃ and the stirring speed of 250 rpm;
and 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle to an aging tank for aging, and then centrifugally washing and drying to obtain the radial nickel-cobalt-manganese precursor Ni with the granularity of 20 mu m0.7Co0.1Mn0.16Mg0.04(OH)2。
2) Preparation of nickel-cobalt-manganese anode material LiNi for doped lithium ion battery0.7Co0.1Mn0.16Mg0.04O2：
The radioactive nickel-cobalt-manganese precursor Ni is0.7Co0.1Mn0.16Mg0.04(OH)2Mixing with a lithium source, and sintering at high temperature for 9h in an atmosphere furnace with 900 ℃ and oxygen to obtain the nickel-cobalt-manganese positive electrode material LiNi for the doped lithium ion battery0.7Co0.1Mn0.16Mg0.04O2(ii) a Wherein the proportion of lithium is 1.05.
Example 6
1) Preparation of Ni-Co-Mn precursor for doped lithium ion battery0.7Co0.1Mn0.17Mg0.03(OH)2；
Step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.17: fully mixing nickel sulfate, cobalt sulfate, manganese sulfate and magnesium sulfate according to the proportion of 0.03 to prepare a mixed salt solution with the concentration of nickel ions, cobalt ions, manganese ions and magnesium ions being 1mol/L for later use;
step 2, respectively adding the mixed salt solution, a sodium hydroxide solution with the concentration of 4mol/L and ammonia water with the concentration of 10mol/L into a reaction kettle through a metering pump in the nitrogen atmosphere, controlling the pH of the system to be 11-12.5 in the feeding process, and then carrying out coprecipitation reaction for 75 hours at the temperature of 55 ℃ and the stirring speed of 200 rpm;
step 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required sizeTransferring the materials in the reaction kettle to an aging tank for aging, and then centrifugally washing and drying to obtain a radial nickel-cobalt-manganese precursor Ni with the particle size of 15 mu m0.7Co0.1Mn0.17Mg0.03(OH)2。
2) Preparation of nickel-cobalt-manganese anode material LiNi for doped lithium ion battery0.7Co0.1Mn0.17Mg0.03O2：
The radioactive nickel-cobalt-manganese precursor Ni is0.7Co0.1Mn0.17Mg0.03(OH)2Mixing with a lithium source, and sintering at high temperature for 11h in an atmosphere furnace with oxygen at 800 ℃ to obtain the nickel-cobalt-manganese positive electrode material LiNi for the doped lithium ion battery0.7Co0.1Mn0.17Mg0.03O2(ii) a Wherein the proportion of lithium is 1.05.
Example 7
1) Preparation of Ni-Co-Mn precursor for doped lithium ion battery0.7Co0.1Mn0.17Mg0.03(OH)2；
Step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.17: fully mixing nickel sulfate, cobalt sulfate, manganese sulfate and magnesium sulfate according to the proportion of 0.03 to prepare a mixed salt solution with the concentration of nickel ions, cobalt ions, manganese ions and magnesium ions being 1mol/L for later use;
step 2, in an inert gas atmosphere, adding the mixed salt solution, a sodium hydroxide solution with the concentration of 3-5 mol/L and ammonia water with the concentration of 5mol/L into a reaction kettle through a metering pump respectively, controlling the pH of the system to be 11-12.5 in the feeding process, and performing coprecipitation reaction for 60 hours at the temperature of 70 ℃ and the stirring speed of 250 rpm;
and 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle to an aging tank for aging, and then centrifugally washing and drying to obtain the radial nickel-cobalt-manganese precursor Ni with the granularity of 15 mu m0.7Co0.1Mn0.17Mg0.03(OH)2。
2) Preparation of Ni-Co-Mn alloy for doped lithium ion batteryPositive electrode material LiNi0.7Co0.1Mn0.17Mg0.03O2：
The radioactive nickel-cobalt-manganese precursor Ni is0.7Co0.1Mn0.17Mg0.03(OH)2Mixing with a lithium source, and sintering at high temperature for 9h in an atmosphere furnace with 900 ℃ and oxygen to obtain the nickel-cobalt-manganese positive electrode material LiNi for the doped lithium ion battery0.7Co0.1Mn0.17Mg0.03O2(ii) a Wherein the proportion of lithium is 1.05.
Example 8
1) Preparation of Ni-Co-Mn precursor for doped lithium ion battery0.7Co0.1Mn0.16Mg0.04(OH)2；
Step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.16: mixing nickel chloride, cobalt chloride, manganese chloride and magnesium chloride fully according to the proportion of 0.04(4:1) to prepare a mixed salt solution with the concentration of nickel, cobalt, manganese and magnesium ions being 3mol/L for later use;
step 2, in an inert gas atmosphere, adding the mixed salt solution, a sodium hydroxide solution with the concentration of 3-5 mol/L and ammonia water with the concentration of 5mol/L into a reaction kettle through a metering pump respectively, controlling the pH of the system to be 11-12.5 in the feeding process, and performing coprecipitation reaction for 60 hours at the temperature of 70 ℃ and the stirring speed of 250 rpm;
and 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle to an aging tank for aging, and then centrifugally washing and drying to obtain the radial nickel-cobalt-manganese precursor Ni with the granularity of 25 mu m0.7Co0.1Mn0.16Mg0.04(OH)2。
2) Preparation of nickel-cobalt-manganese anode material LiNi for doped lithium ion battery0.7Co0.1Mn0.16Mg0.04O2：
The radioactive nickel-cobalt-manganese precursor Ni is0.7Co0.1Mn0.16Mg0.04(OH)2Mixing with lithium source, and introducing oxygen at 800 deg.CSintering the mixture for 11 hours at high temperature in a gas atmosphere furnace to obtain the nickel-cobalt-manganese anode material LiNi for the doped lithium ion battery0.7Co0.1Mn0.16Mg0.04O2(ii) a Wherein the proportion of lithium is 1.05.
Example 9
1) Preparation of Ni-Co-Mn precursor for doped lithium ion battery0.7Co0.1Mn0.08Mg0.02(OH)2；
Step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.18: 0.02(9:1), fully mixing nickel nitrate, cobalt nitrate, manganese nitrate and magnesium nitrate to prepare a mixed salt solution with the concentration of nickel, cobalt, manganese and magnesium ions being 3mol/L for later use;
step 2, in an inert gas atmosphere, adding the mixed salt solution, a sodium hydroxide solution with the concentration of 3mol/L and ammonia water with the concentration of 8mol/L into a reaction kettle through a metering pump respectively, controlling the pH of the system to be 11-12.5 in the feeding process, and then carrying out coprecipitation reaction for 90 hours at the temperature of 40-70 ℃ and the stirring speed of 150 rpm;
and 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle to an aging tank for aging, and then centrifugally washing and drying to obtain the radial nickel-cobalt-manganese precursor Ni with the granularity of 25 mu m0.7Co0.1Mn0.08Mg0.02(OH)2。
2) Preparation of nickel-cobalt-manganese anode material LiNi for doped lithium ion battery0.7Co0.1Mn0.18Mg0.02O2：
The radioactive nickel-cobalt-manganese precursor Ni is0.7Co0.1Mn0.08Mg0.02(OH)2Mixing with a lithium source, and sintering at high temperature for 14h in an atmosphere furnace with 700 ℃ and oxygen to obtain the nickel-cobalt-manganese positive electrode material LiNi for the doped lithium ion battery0.7Co0.1Mn0.18Mg0.02O2(ii) a Wherein the proportion of lithium is 1.05.
Assembling a button cell and detecting:
the nickel-cobalt-manganese positive electrode material for the doped lithium ion battery obtained in examples 1 to 9 was used as a positive electrode, and a metal lithium plate was used as a negative electrode, and the nickel-cobalt-manganese positive electrode material and the metal lithium plate were respectively assembled into 9 button cells to perform a charge-discharge comparative test, and the test results were as follows:
table 1 shows specific discharge capacity test data of the positive electrode materials of the batteries obtained in examples 1 to 9 and the positive electrode material of the conventional battery
From table 1, it can be derived: by adopting the anode material as the anode and the metal lithium sheet as the cathode to assemble the button cell for charge-discharge comparative test, the initial discharge specific capacity can reach 198mAh/g under the multiplying power of 0.5C, the capacity retention rate can reach 98.7 percent after 100 charge-discharge cycles, while the initial discharge specific capacity of the common anode material is 183mAh/g, and the capacity retention rate is 96.2 percent after 100 charge-discharge cycles; therefore, the specific discharge capacity of the battery prepared from the nickel-cobalt-manganese anode material for the doped lithium ion battery is superior to that of the battery prepared from the conventional battery anode material.
According to the scheme of the invention, the Mg doping element is directly added in the coprecipitation process, so that the doping element can be uniformly distributed in the precursor particles, the modification effect of the doping element is effectively exerted, and the magnesium doping is beneficial to forming a good layered structure, enhancing the structural stability of the material and improving the cycle performance of the high-nickel ternary material. By controlling the synthesis process of the precursor, primary particles are directionally arranged to form a radial structure from inside to outside, and the precursor particles grow radially from inside to outside, so that the lithium salt is favorably diffused in the precursor particles in the sintering process for preparing the anode material, the reaction is more sufficient, the prepared ternary anode material can form a lithium ion diffusion channel from inside to outside, the radial structure is favorable for the extraction and the insertion of lithium ions, and the particle structure is more stable, so that the excellent electrochemical performance is shown.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The nickel-cobalt-manganese precursor for the doped lithium ion battery is characterized by being a radioactive metal hydroxide, and having the chemical expression as follows: ni0.7Co0.1Mn0.2-xMgx(OH)2Wherein x is more than or equal to 0.02 and less than or equal to 0.04.
2. The nickel-cobalt-manganese precursor for the doped lithium ion battery according to claim 1, wherein the average particle size of the nickel-cobalt-manganese precursor for the doped lithium ion battery is 15-25 μm.
3. A positive electrode material for a lithium ion battery having the precursor of claim 1, wherein the positive electrode material has a molecular formula of LiNi0.7Co0.1Mn0.2-x MgxO2Wherein x is more than or equal to 0.02 and less than or equal to 0.04.
4. A method for preparing the nickel-cobalt-manganese precursor for the doped lithium ion battery according to claim 1 or 2, wherein the method comprises the following steps:
step 1, mixing the components in a molar ratio of Ni: co: (Mn + Mg) 7: 1: 2 and Mn: mg is 0.2-x: x (x is more than or equal to 0.02 and less than or equal to 0.04) is fully mixed with nickel salt, cobalt salt, manganese salt and magnesium salt to prepare a mixed salt solution for later use;
step 2, respectively adding the mixed salt solution, the alkali solution and the ammonia water in the step 1 into a reaction kettle in an inert gas atmosphere, and carrying out coprecipitation reaction under stirring;
step 3, when the granularity of the precursor particles in the reaction kettle reaches the required size, stopping the reaction, and transferring the materials in the reaction kettle to an ageing tankPerforming middle aging, then centrifugally washing and drying to obtain a radioactive nickel-cobalt-manganese precursor Ni0.7Co0.1Mn0.2-xMgx(OH)2。
5. The method according to claim 4, wherein in step 1, the nickel salt is at least one of nickel chloride, nickel sulfate and nickel nitrate; the cobalt salt is at least one of cobalt chloride, cobalt sulfate and cobalt nitrate; the manganese salt is at least one of manganese chloride, manganese sulfate and manganese nitrate; the magnesium salt is at least one of magnesium chloride, magnesium sulfate and magnesium nitrate.
6. The method according to claim 5, wherein in the step 1, the concentration of nickel, cobalt, manganese and magnesium ions in the mixed salt solution is 1-3 mol/L.
7. The method for preparing the nickel-cobalt-manganese precursor for the doped lithium ion battery according to claim 6, wherein in the step 2, the molar concentration of the alkali solution is 3-5 mol/L, and the molar concentration of the ammonia water is 8-12 mol/L; the alkali in the alkali solution is sodium hydroxide or potassium hydroxide.
8. The method for preparing the nickel-cobalt-manganese precursor for the doped lithium ion battery according to any one of claims 4 to 7, wherein in the step 2, the reaction temperature of the coprecipitation reaction is 40 to 70 ℃, the reaction pH is 11 to 12.5, the stirring speed is 150 to 250rpm, and the reaction time is 60 to 90 hours.
9. The method for preparing the nickel-cobalt-manganese positive electrode material for the doped lithium ion battery according to claim 3, wherein the method comprises the following steps: mixing the precursor prepared by the preparation method of any one of claims 4 to 8 with a lithium source, and sintering at high temperature in an atmosphere furnace filled with oxygen to obtain doped lithium ionsNickel-cobalt-manganese positive electrode material LiNi for sub-battery0.7Co0.1Mn0.2-x MgxO2。
10. The method for preparing the nickel-cobalt-manganese positive electrode material for the doped lithium ion battery according to claim 9, wherein the ratio of lithium is 1.05, the sintering temperature is 700-900 ℃, and the sintering time is 9-14 h.
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